CN114272156A - Oil-removing fluffy washing-free hair drying spray and preparation method thereof - Google Patents
Oil-removing fluffy washing-free hair drying spray and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a deoiling fluffing washing-free hair drying spray and a preparation method thereof. The preparation method comprises the following steps: preparing starch raw pulp from rice starch, and adding amylase for enzymolysis to obtain a starch granule core; mixing the starch granule core and the high-activity polyether polyol, and then reacting with an isocyanate substance to obtain oil-absorbing granules; the oil-absorbing particles are used as important components to prepare oil-removing washing-free hair-drying spray. The oil-removing fluffy washing-free dry hair spray has good oil absorption effect and quick particle dissipation after being sprayed; is not easy to generate various phenomena of agglomeration, aggregation and reunion, basically does not generate refraction effect, and does not have whitening phenomenon.
Description
Technical Field
The invention relates to a washing-free hair drying spray for removing oil and relaxing hair and a preparation method thereof, belonging to the technical field of daily chemical industry.
Background
The shampoo is an essential daily product for hair cleaning and scalp basic care in daily life. When in use, a large amount of clear water is needed to soak, rub and clean the hair; if necessary, the wet hair is quickly dried to prevent cold. The desire to clean hair is difficult to satisfy at night, after sports, people feel full of sweat, people have inconvenience in bathing outdoors, have grown up, are ill and hospitalized, travel outdoors and … … are always special.
At present, a plurality of hair dry-cleaning sprays are available on the market, and can conveniently, quickly and quickly clean greasy hair attached with various dirt into a fluffy and dry state. Particularly, a plurality of products have additional fresh smells, are very popular in some European and American countries, and are gradually accepted by domestic markets in recent years. For example, in chinese patent application No. 201810871215.9, an aerosol for dry hair is disclosed. It uses rice starch, modified starch and silica as main oil-absorbing components, and matches it with a certain surfactant and other auxiliary components, and can dry-clean hair without water.
At present, the hair dry-cleaning spray sold in the market has the using effect of barely achieving the states of oil absorption and oil removal, but the effect is not completely ideal. In order to achieve better oil absorption and oil removal effects, a sufficient amount of oil removal components needs to be sprayed. When in spraying, the oil-absorbing oil is easily sprayed on the skin surface of the head and face, so that the skin feel is poor, and the whole makeup is damaged. When a sufficient amount of spray is used, the whole hair is often in an unnatural stiff and hard state, and the visual effect of the sprayed hair at the center part can also be whitened (for example, fig. 1 shows the actual using effect of the existing oil-removing dry hair spray product which is sold well, and the white part after spraying can be obviously seen). According to practical operation experience, after the oil absorption particles and dirt of part of the commercial products are agglomerated and agglomerated, the effects similar to the effects of fine powder and dandruff can be generated, and the appearance is very unattractive. These products can only satisfy the requirement of "oil removal" in a certain sense, but cannot achieve the effect of refreshing the overall image of a human body.
Disclosure of Invention
The invention aims to solve the primary technical problem of providing a preparation method of oil-removing fluffy washing-free hair drying spray.
The invention aims to solve another technical problem of providing the oil-removing fluffy washing-free hair drying spray.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to a first aspect of embodiments of the present invention, there is provided a method of preparing a greasy fluffy leave-on dry hair spray, wherein the preparation of the oil absorbing particles for use in the dry hair spray comprises the steps of:
(1) preparing starch granules;
step 1: prefabricated starch raw stock
Mixing and stirring 100 parts of rice starch and 200-300 parts of purified water, heating to 45-50 ℃, and carrying out heat preservation and stirring treatment for 15-30 minutes to prepare starch raw stock;
step 2: enzymolysis
Adjusting the pH value of the starch raw stock prepared in the step 1 to 5.0-6.0, adding 0.1 part of alpha-amylase, keeping the constant temperature at 40 ℃, and stirring for reacting for 1-2 hours; centrifuging to obtain supernatant and precipitate, washing the precipitate with clear water, and centrifuging; until the supernatant is neutral; removing supernatant, heating the precipitate to 100 deg.C, and maintaining for 10 min to ensure enzyme deactivation;
blowing and drying at the constant temperature of 45 ℃ to prepare a starch granule core;
(2) a starch granule core polymerization product;
and step 3: premixing
Preheating a sealed reaction kettle, removing water, adding 5-10 parts by weight of high-activity polyether polyol into 100 parts by weight of a starch granule core under the protection of nitrogen, heating to 105 ℃, dispersing and stirring at a high speed, vacuumizing and dehydrating for 1 hour, and cooling to room temperature;
and 4, step 4: mixing reaction
Slowly adding isocyanate substances into a sealed reaction kettle, stirring and dispersing for 30 minutes, heating to 50 ℃ under stirring at a rotating speed of more than 200rpm, reacting for 1 hour, heating to 90 ℃, keeping stirring, reacting for 3 hours, and cooling to room temperature;
and 5: obtaining the oil absorption particle finished product
Filtering the product after cooling to room temperature by using a 100-mesh filter screen to obtain white microsphere particles with the solid content of more than 99.5 percent; drying in a vacuum drying oven for more than 30 minutes to obtain particles with the particle size of 0.1-30 microns, and taking the particles as a finished product of oil absorption particles of the deoiling fluffy washing-free hair drying spray.
Preferably, the high-activity polyether polyol is: polypropylene glycol having a number average molecular weight of 500 to 4000; or polyoxypropylene triol with the number average molecular weight of 2000-3000; or the number average molecular weight is 1000-3000; alternatively, a polycaprolactone polyol product prepared from epsilon-caprolactone and trimethylolpropane polyether.
Wherein, the isocyanate substance is preferably any one or more of toluene diisocyanate, diphenylmethane diisocyanate, 4' -diisocyanate dicyclohexylmethane, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
Wherein the isocyanate material is preferably a modified polyisocyanate having an isocyanurate group of 3 or more based on one or more of toluene diisocyanate, diphenylmethane diisocyanate, 4' -diisocyanate dicyclohexylmethane, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
Preferably, in the step 3: in the premixing, 2 parts of silane coupling agent is added into the core of the starch granule, and after the starch granule is uniformly stirred and mixed, the high-activity polyether glycol is added.
Preferably, in the step 4: the number of isocyanate groups of the isocyanate substance added in the mixing reaction and the number of hydroxyl groups of the high-activity polyether polyol added in the step 3 are respectively 1.05-1.10 in the theoretical value ratio.
Preferably, in the step 4: when the isocyanate material added in the reaction was mixed, 1 wt% of N, N-dimethylformamide was previously mixed.
Wherein the particle size of the oil absorption particles is preferably in the range of 0.1-30 microns.
Wherein preferably, the oil absorption rate of the oil absorption particles is 60g/100 g-81 g/100 g.
According to a second aspect of embodiments of the present invention there is provided a de-oiled voluminous leave-in dry hair spray comprising the following components: 3-10 parts of oil absorption particles; 0.5 part of butanediol; 0.5 part of glycerol; 0.5 part of EDTA disodium; 0.2 part of cetrimide; 0.2 part of tridecyl alcohol polyether-10; the balance being propellant.
Firstly, preparing a starch granule core, adsorbing polyol by using physical adsorption, and simultaneously carrying out cross-linking polymerization reaction on the polyol and the isocyanate; the final crosslinked polymer product (after reaction of hydroxyl and isocyanate groups) had the morphology: the starch granules are partially embedded and partially wrapped inside and outside the starch granules, the whole particles are in a sphere-like shape, the outer surface of the whole particles has no acute angle or bulge, the particles are basically smooth, the particle size is basically distributed within the range of 1-20 micrometers, and more than 50% of the particle size is distributed between 5-10 micrometers.
Compared with the common starch or modified starch which is insufficient in oil absorption, the white gray light reflecting state is easy to appear; the oil-absorbing particles and dirt remain on the hair and cannot improve the tangled, collapsed state of the hair. The oil absorption capacity of the oil absorption fluffy particles prepared by the invention is obviously improved, and various dirt attached to the hair can be completely, quickly and effectively adsorbed. Most of the oil-absorbing fluffy particles prepared by the invention have the particle size range of not more than 20 microns, so that the product generated after the particles adsorb dirt on hair can be avoided, the poor visual effect of whitening and grayish white light reflection is not easy to form, and the experience feeling of the product is higher.
Drawings
FIG. 1 is a schematic diagram showing the effect of a no-clean oil-removing dry hair spray on the market;
FIG. 2 is an SEM electron micrograph of a common starch granule;
FIG. 3 is an SEM electron micrograph of starch granules of an HDI/trimethylol hexyl lactone cross-linked polymer;
FIG. 4 is a schematic diagram showing the hydrophobic effect of the starch granules prepared according to the present invention.
Detailed Description
The technical contents of the invention are described in detail below with reference to the accompanying drawings and specific embodiments.
In the process of preparing the oil-removing fluffy wash-free hair drying spray provided by the invention, oil-absorbing particles used by the hair drying spray are firstly required to be prepared. The preparation process of the oil-absorbing particle comprises the following steps:
(1) and (3) preparing starch granules.
Step 1: prefabricated starch raw stock
Mixing and stirring 100 parts of rice starch and 200-300 parts of purified water, heating to 45-50 ℃, and carrying out heat preservation and stirring treatment for 15-30 minutes to prepare the starch raw stock.
Generally, the grain starch granule is mainly provided with amylopectin at the center and amylose and esters at the periphery. Under the condition of the step, the water absorption process of the starch granules is reversible, and a small amount of water is absorbed to have certain expansion, so that the subsequent treatment is convenient.
Step 2: enzymolysis
And (2) adjusting the pH value of the starch raw stock prepared in the step (1) to 5.0-6.0, adding 0.1 part of alpha-amylase (the activity is more than or equal to 50U/mg), keeping the constant temperature at 40 ℃, and stirring for reacting for 1-2 hours. Centrifuging to obtain supernatant and precipitate, washing the precipitate with clear water, and centrifuging; until the supernatant was determined to be neutral.
The supernatant was skimmed off and the precipitate was heated to 100 ℃ for 10 minutes to ensure enzyme deactivation.
And (3) blowing and drying at the constant temperature of 45 ℃ to prepare the starch granule core.
The prepared starch granule core strengthens the space gap and partial surface structure in the starch granule, so that the starch granule can conveniently adsorb enough reagents in subsequent reaction and further effectively react. The starch subjected to enzymolysis treatment enhances the opening effect and further enhances the adsorption capacity. After enzymatic hydrolysis, the mechanical strength of the starch granules may be slightly reduced by heating to 100 ℃ to inactivate the enzyme. In the subsequent cross-linking polymerization reaction, there may be a portion of the particles that may be further broken down, resulting in a small particle size particle fraction in the final product.
(2) Starch granule core polymerization product.
And step 3: premixing
Preheating a sealed reaction kettle, removing water, adding 5-10 parts by weight of high-activity polyether polyol into 100 parts by weight of the starch granule core under the protection of nitrogen, heating to 105 ℃, stirring at high speed (1000rpm), vacuumizing (below 0.05 MPA), dehydrating for 1 hour, and cooling to room temperature.
Preferably, in the reaction kettle, 2 parts of silane coupling agent is added into the core of the starch granules, and after the mixture is stirred and mixed uniformly, the high-activity polyether polyol is added, so that the starch granules can be mixed and absorbed favorably.
Specifically, the silane coupling agent adopts an aminosilane coupling agent KH550 (Xuzhou bright Huiyang new material); the active groups are favorable for the mutual cross-linking polymerization among starch granules, polyol, isocyanate and the like, and are coated in and on the core pores of the granules.
The high-activity polyether polyol is:
polypropylene glycol having a number average molecular weight of 500 to 4000;
specifically selecting: polypropylene glycol PPG4000 (xu bright huiyang new material) with a number average molecular weight of 4000; polypropylene glycol PPG1000 (xu bright hui new material) with a number average molecular weight of 1000, polypropylene glycol PPG400 (xu bright hui new material) with a number average molecular weight of 400;
or polyoxypropylene triol with the number average molecular weight of 2000-3000;
specifically selecting: polyoxypropylene triol with number average molecular weight of 3000 (xu bright huiyang new material);
or the number average molecular weight is 1000-3000;
specifically selecting: a bis-alcoholic hydroxyl group mono-terminated silicone oil 8861 (Anhui Ming Yi Silicones) having a number average molecular weight of 1300;
or, a polycaprolactone polyol product prepared from epsilon-caprolactone and trimethylolpropane polyether;
epsilon-caprolactone PCL-2044 (Hunan Polymer chemical) with the number average molecular weight of 400; epsilon-caprolactone PCL-2200A (Hunan Polymer chemical) with a number average molecular weight of 2000.
And 4, step 4: mixing reaction
Slowly adding isocyanate substance into a sealed reaction kettle, wherein the ratio of isocyanate group to hydroxyl is more than 1, stirring and dispersing for 30 minutes, then heating to 50 ℃ under the stirring of the rotating speed of more than 200rpm, reacting for 1 hour, heating to 90 ℃, keeping stirring, reacting for 3 hours, and cooling to room temperature.
The isocyanate substance is any one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4' -diisocyanate dicyclohexylmethane (HMDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI); all manufacturers are in all China.
The isocyanate material may also be a modified polyisocyanate having 3 or more isocyanurate groups based on one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4' -diisocyanate dicyclohexylmethane (HMDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI) prepared by modifying the above isocyanate material.
Specifically, since the reactive groups of the isocyanate and reactive polyether polyol starting materials are liable to undergo side reactions, only the theoretical values of the starting materials are considered. The ratio of the theoretical value of the number of isocyanate groups of the isocyanate substance added in the step 4 to the theoretical value of the number of hydroxyl groups of the high-activity polyether polyol added in the step 3 is controlled to be 1.05-1.10.
Wherein, preferably, 1 wt% of N, N-Dimethylformamide (DMF) is mixed in advance when the isocyanate substance is added, and particularly, when the molecular weight of the polyether polyol is more than 3000, and the viscosity of the matched isocyanate substance is higher, the crosslinking polymerization reaction can be effectively promoted.
And 5: obtaining the oil absorption particle finished product
And filtering the product after cooling to room temperature by using a 100-mesh filter screen to obtain white microsphere particles with the solid content of more than 99.5 percent. Drying for more than 30 minutes in a vacuum drying oven at 70 ℃ to obtain particles with the particle size of 0.1-30 microns, and taking the particles as a finished product of oil absorption particles of the deoiling fluffy washing-free hair drying spray raw material.
In the embodiment of the invention, the starch granule core subjected to enzymolysis and fermentation can effectively adsorb high-activity polyether polyol (or similar substances).
When heating, partial high-activity polyether polyol (or similar substances) may generate side reaction, and a small amount of long chain generates polyether chain breakage, ring opening, partial group shedding and the like, so that more-OH groups are exposed, and the system actually contains-OH groups exceeding the theoretical value, possibly reaching 105 percent of the theoretical value. Meanwhile, after the starch granules are subjected to enzymolysis and fermentation treatment, partial branched chains are broken, partial hydrolysis is carried out, a small amount of side reaction can also occur, and the surfaces of the starch granules also have a small amount of stable free-OH groups.
Thus, in step 4, the target product is predominantly-NCO-blocked, requiring the addition of an isocyanate group to hydroxyl ratio of greater than 1.05, but generally not greater than 1.10.
In the whole system, various-OH groups react with-NCO groups of isocyanate substances, treated starch particles are taken as a basic core, the silane coupling agent increases the adsorption force and active groups on the inner surface and the outer surface of the starch particles, polyether polyol substances and the isocyanate substances generate crosslinking reaction products, and the crosslinking reaction products are polymerized and coated on the surfaces of the starch particles or in partial shallow pores to form the appearance of the finished product oil absorption particles which are relatively nearly spherical. In the process of physical adsorption by starch particles and side reaction with a silane coupling agent, the isocyanate groups participating in the reaction also have complex cross-linking and polymerization reactions with-OH groups or other active groups from various sources.
The surface free groups of the finished oil-absorbing particles are detected to have mainly-NCO end capping, and simultaneously contain a small amount of-OH groups which may be derived from polyether polyols (or ring-opening and open-chain derived products thereof) and a small amount of free-state-OH groups derived from the starch particles. Detecting that various oil absorption particle products possibly contain 1-3% of exposed-NCO groups and 3-5% of exposed-OH groups according to theoretical values; these groups all have some activity but do not participate in the reaction.
The surface of the finished oil absorption particle is provided with the two active groups, so that no further reaction occurs in a relatively stable environment, and the activity is maintained for a long time. After being sprayed on the hair surface, the hair cleaning agent can quickly react with dirt, grease and other components on the hair surface to absorb and adsorb the grease dirt. On the other hand, the finished oil absorption particles also have the strong adsorption capacity of the original starch particles, the structure is complete, and the oil absorption particles also have good mechanical strength in a dry state; is very useful for adsorbing a mixture of various substances including dust, debris, fibers, sebum secretion, moisture, and the like.
Detecting a plurality of oil-absorbing particles, wherein the oil absorption rate is about 55-83 g/100 g. This is much higher than the untreated ordinary rice starch oil absorption of 47.3g/100g, and also higher than the main oil absorption component of the common hair drying spray: the oil absorption of aluminum starch octenyl succinate (conventional modified starch) was 31.9g/100 g.
And (3) observing the morphology of the oil absorption particles: as shown in FIG. 3, the particles are approximately spherical as a whole, smooth in outer surface, low in aggregation state and excellent in dispersibility, and particularly, particles having a small particle diameter (between 0.5 and 4 μm) are also spherical, and the proportion of the small particle diameter is small, and generally 20% or less. A marked difference from the angular irregularity of the original starch granules (fig. 2). The particle size distribution of the oil absorption particles is mainly 0.1-30 microns, wherein more than 50% of the particle sizes are 4-7 microns. As shown in fig. 4, the oil-absorbing particles float directly on the water surface, and have very obvious strong hydrophobicity.
The oil-absorbing particles are used as main components to prepare the finished dry hair spray. Storing in a tank and standing for more than 6 months; the oil absorption particles can still be kept in a state of no agglomeration, no agglomeration and high dispersibility, and can not block the nozzle, and the using effect is not broken. On the other hand, the oil absorption particles are nearly spherical regardless of particle size, smooth in surface and high in dispersibility, and can naturally eliminate accumulation and agglomeration when being sprayed to the surface of the head. Direct condition of applied non-combed hair as shown: after the hair is brushed, a little bit of white mark can be seen slightly, and the mark can not be seen immediately after the hair is combed for a few times. This completely avoids the accumulation of oil-absorbing particles at the direct spray site, which can result in significant white powder agglomeration on the hair surface, similar to dandruff or dirt, which can still exhibit an aesthetically-affecting "whitening" phenomenon with multiple combing.
Preparation of starch granules example 1:
step 1: prefabricated starch raw stock
Mixing and stirring 100 parts of rice starch and 200 parts of purified water, heating to 45 ℃, preserving heat and stirring for 15 minutes to prepare the starch raw stock.
Step 2: enzymolysis
And (3) adjusting the pH value of the starch raw stock prepared in the step (1) to 5.5, adding 0.1 part of alpha-amylase (the activity is more than or equal to 50U/mg), keeping the constant temperature at 40 ℃, and stirring for reacting for 1 hour. Centrifuging to separate supernatant and precipitate, washing precipitate with water, and centrifuging; until the supernatant was determined to be neutral. The precipitate was heated to 100 ℃ for 10 minutes to ensure enzyme deactivation.
And air-drying at a constant temperature of 45 ℃ to prepare a starch granule core sample 1.
Preparation of starch granules example 2:
step 1: prefabricated starch raw stock
Mixing and stirring 100 parts of rice starch and 300 parts of purified water, heating to 50 ℃, preserving heat and stirring for 30 minutes to prepare the starch raw stock.
Step 2: enzymolysis
And (3) adjusting the pH value of the starch raw stock prepared in the step (1) to 6.0, adding 0.1 part of alpha-amylase (the activity is more than or equal to 50U/mg), keeping the constant temperature at 40 ℃, and stirring for reacting for 2 hours. Centrifuging to separate supernatant and precipitate, washing precipitate with water, and centrifuging; until the supernatant was determined to be neutral. The precipitate was heated to 100 ℃ for 10 minutes to ensure enzyme deactivation.
And air-drying at a constant temperature of 45 ℃ to prepare a starch granule core sample 2.
Preparation of leave-on oil-absorbing particles for dry hair spray example 1:
and step 3: premixing
Preheating a sealed reaction kettle, removing water, selecting and premixing 2 parts of silane coupling agent in 100 parts by weight of 1 or 2 starch granule core samples or common starch granules in a nitrogen protective atmosphere, uniformly stirring, respectively adding 5-10 parts of high-activity polyether polyol, heating to 105 ℃, dispersing at a high speed (1000rpm), stirring, vacuumizing (below 0.05 MPA), dehydrating for 1 hour, and cooling to room temperature.
And 4, step 4: mixing reaction
The isocyanate substance is slowly added into the sealed reaction kettle, and N, N-Dimethylformamide (DMF) with the weight of 1 wt% can be selected to be mixed in advance. The ratio of isocyanate groups added to hydroxyl groups added in step 1 was 1.05. Stirring and dispersing for 30 minutes, heating to 50 ℃ under stirring at the rotating speed of more than 200rpm, reacting for 1 hour, heating to 90 ℃, keeping stirring, reacting for 3 hours, and cooling to room temperature.
And 5: obtaining the oil absorption particle finished product
And filtering the product after cooling to room temperature by using a 100-mesh filter screen to obtain white microsphere particles with the solid content of more than 99.5 percent. Drying in vacuum oven at 70 deg.C for more than 30 min to obtain granule as raw material for no-wash hair drying spray.
100 parts by weight of a starch granule core sample 1 is taken as a core, and the high-activity polyether polyol is specifically matched as follows:
firstly, 2 parts by weight of silane coupling agent KH550 is added, and then 10 parts by weight of polypropylene glycol PPG4000 with the number average molecular weight of 4000 is added;
5 parts by weight of polypropylene glycol PPG1000 having a number average molecular weight of 1000;
6 parts by weight of polypropylene glycol PPG400 having a number average molecular weight of 400;
firstly, 2 parts by weight of silane coupling agent KH550 is added, and 8 parts by weight of polyoxypropylene triol with the number average molecular weight of 3000 is added;
10 parts by weight of a bis (alcoholic hydroxyl) mono-terminated silicone oil 8861 with a number average molecular weight of 1300;
a product prepared from 6 parts by weight of epsilon-caprolactone (polycaprolactone triol) and trimethylolpropane polyether.
The isocyanate is specifically: toluene Diisocyanate (TDI) 1.05 times the theoretical number of hydroxyl groups, diphenylmethane diisocyanate (MDI) 1.06 times, dicyclohexylmethane (HMDI) 4.08 times the theoretical number of hydroxyl groups, hexamethylene 1, 6-diisocyanate (HDI) 1.05 times the theoretical number of hydroxyl groups, isophorone diisocyanate (IPDI) 1.10 times the theoretical number of hydroxyl groups.
Respectively detecting as follows:
100 parts of common starch granules which are not subjected to enzymolysis and fermentation treatment are taken as cores, and the oil absorption rate of the oil absorption fluffy particles is directly prepared by the common starch granules and 5 parts of polypropylene glycol PPG1000 and Toluene Diisocyanate (TDI) which is 1.05 times of the theoretical value of hydroxyl. Most of PPG and TDI in the system are directly reacted and are not coated on starch granules.
The oil absorption rate of a starch granule core sample 1 prepared by matching KH550 serving as a silane coupling agent with polypropylene glycol PPG4000 and diphenylmethane diisocyanate (MDI) is as follows: 69.2g/100 g; the particle size range is 0.5-22.0 microns; the proportion of particles with the particle size of 4-7 microns is 63%.
The oil absorption of the core sample 1 of starch granules prepared from polypropylene glycol PPG1000 and 1, 6-Hexamethylene Diisocyanate (HDI) was: 73.1g/100 g; the particle size range is 0.3-24.5 microns; the proportion of particles between 4 and 7 microns is 55 percent.
The oil absorption of the starch granule core sample 1 prepared from polypropylene glycol PPG400 and isophorone diisocyanate (IPDI) is: 81.2g/100 g; the particle size range is 0.3-26.7 microns; the proportion of particles with the particle size of 4-7 microns is 45%.
The oil absorption of a starch granule core sample 1 prepared from KH550 part, polyoxypropylene triol complexed with 4, 4' -diisocyanate dicyclohexylmethane (HMDI), was: 79.6g/100 g; the particle size range is 0.6-28.1 microns; the proportion of particles with the particle size of 4-7 microns is 62%.
The oil absorption of the starch particle core sample 1 prepared from a bishydroxy-terminated silicone oil 8861 and 1, 6-Hexamethylene Diisocyanate (HDI) previously mixed with 1% by weight of N, N-Dimethylformamide (DMF) was: 67.9g/100 g; the particle size range is 0.3-22.8 microns; the proportion of particles with the particle size of 4-7 microns is 48%.
Silane coupling agent part KH550 compounded with polypropylene glycol PPG1000 and starch particle core sample 2 prepared by premixing 1 wt% of N, N-Dimethylformamide (DMF)4, 4' -diisocyanate dicyclohexylmethane (HMDI) had an oil absorption of: 77.5g/100 g; the particle size range is 0.1-30.3 microns; the proportion of particles with the particle size of 4-7 microns is 71%.
The oil absorption of the product prepared from epsilon-caprolactone and trimethylolpropane polyether and starch granule core sample 1 with 1, 6-Hexamethylene Diisocyanate (HDI) as the HDI/trimethylolhexyllactone crosspolymer was: 77.5g/100 g; the particle size range is 0.4-28.6 microns; the proportion of particles with the particle size of 4-7 microns is 68%.
The oil absorption rate of a starch particle core sample 2 prepared from KH550 serving as a silane coupling agent, dihydric alcohol hydroxyl single-terminated silicone oil 8861 and diphenylmethane diisocyanate (MDI) is as follows: 69.6g/100 g; the particle size range is 0.3-25.7 microns; the content of particles with the particle diameter of 4-7 microns is 53%.
The oil absorption of starch granule core sample 2 prepared from polyoxypropylene triol and Toluene Diisocyanate (TDI) was: 60.4g/100 g; the particle size range is 1.5-28.5 microns; the proportion of particles with the particle size of 4-7 microns is 47%.
The oil absorption of the starch granule core sample 2 prepared from polypropylene glycol PPG1000 and isophorone diisocyanate (IPDI) is: 67.3g/100 g; the particle size range is 0.1-25.6 microns; the proportion of particles between 4 and 7 microns is 55 percent.
The oil absorption of the starch particle core sample 2 prepared by compounding 8861 a bis-alcoholic hydroxyl group mono-blocked silicone oil and 1 wt% N, N-Dimethylformamide (DMF)4, 4' -diisocyanate dicyclohexylmethane (HMDI) in advance was: 80.5g/100 g; the particle size range is 0.1-30.3 microns; the proportion of particles with the particle size of 4-7 microns is 71%.
The oil absorption of sample 2, a core starch particle made from the product of epsilon-caprolactone and trimethylolpropane polyether and 1, 6-Hexamethylene Diisocyanate (HDI) as a HDI/trimethylolhexyllactone crosspolymer, was: 71.7g/100 g; the particle size range is 0.2-23.4 microns; the proportion of particles with the particle size of 4-7 microns is 66%.
Preparation of leave-on hair spray example 1:
the oil-removing fluffy washing-free hair drying spray comprises the following components in 100 parts by weight:
3-10 parts of oil absorption particles; 0.5 part of butanediol; 0.5 part of glycerol; 0.5 part of EDTA disodium; 0.2 part of cetrimide; 0.2 part of tridecyl alcohol polyether-10; the balance being propellant (isobutane).
Respectively taking the prepared oil absorption particles as raw material components to prepare dry hair spray. Please 20 testers (no shampooing for at least 4 days) for the test.
The oil-absorbing fluffy particles after spraying almost disappear very quickly when observed by naked eyes under different light conditions (natural light, indoor key illumination light and the like), which is probably because the dispersion performance of the particles is good and the dissipation is quick; on the other hand, after the particles are sprayed, the oil-absorbed product formed on the surface of the hair is not easy to generate various phenomena of agglomeration, aggregation and reunion, and the overall particle size of dirt particles after dirt adsorption is generally less than 20 microns and generally not more than 30 microns, so that the dirt particles are difficult to detect visually. After the oil stain, the water, the simulation dust and the oil absorption fluffy particles are mixed together, the refraction effect of the dirt particles is basically not generated, and the obvious visual effect is not caused. When in testing, the test paper is consistently favored by testers.
The de-oiling fluffy leave-in dry hair spray and the preparation method thereof provided by the invention are explained in detail above. It will be apparent to those skilled in the art that any obvious modifications thereof can be made without departing from the spirit of the invention, which infringes the patent right of the invention and bears the corresponding legal responsibility.
Claims (10)
1. A preparation method of oil-removing fluffy washing-free hair drying spray is characterized in that the preparation of oil-absorbing particles used by the hair drying spray comprises the following steps:
(1) preparing starch granules;
step 1: prefabricated starch raw stock
Mixing and stirring 100 parts of rice starch and 200-300 parts of purified water, heating to 45-50 ℃, and carrying out heat preservation and stirring treatment for 15-30 minutes to prepare starch raw stock;
step 2: enzymolysis
Adjusting the pH value of the starch raw stock prepared in the step 1 to 5.0-6.0, adding 0.1 part of alpha-amylase, keeping the constant temperature at 40 ℃, and stirring for reacting for 1-2 hours; centrifuging to obtain supernatant and precipitate, washing the precipitate with clear water, and centrifuging; until the supernatant is neutral; removing supernatant, heating the precipitate to 100 deg.C, and maintaining for 10 min to ensure enzyme deactivation;
blowing and drying at the constant temperature of 45 ℃ to prepare a starch granule core;
(2) a starch granule core polymerization product;
and step 3: premixing
Preheating a sealed reaction kettle, removing water, adding 5-10 parts by weight of high-activity polyether polyol into 100 parts by weight of a starch granule core under the protection of nitrogen, heating to 105 ℃, dispersing and stirring at a high speed, vacuumizing and dehydrating for 1 hour, and cooling to room temperature;
and 4, step 4: mixing reaction
Slowly adding isocyanate substances into a sealed reaction kettle, stirring and dispersing for 30 minutes, heating to 50 ℃ under stirring at a rotating speed of more than 200rpm, reacting for 1 hour, heating to 90 ℃, keeping stirring, reacting for 3 hours, and cooling to room temperature;
and 5: obtaining the oil absorption particle finished product
Filtering the product after cooling to room temperature by using a 100-mesh filter screen to obtain white microsphere particles with the solid content of more than 99.5 percent; drying in a vacuum drying oven for more than 30 minutes to obtain particles with the particle size of 0.1-30 microns, and taking the particles as oil absorption particles for preparing oil-removing fluffy washing-free hair drying spray.
2. A process for preparing a leave-on hair spray drying oil fluff according to claim 1 wherein the high activity polyether polyol is: polypropylene glycol having a number average molecular weight of 500 to 4000; or polyoxypropylene triol with the number average molecular weight of 2000-3000; or the number average molecular weight is 1000-3000; alternatively, a polycaprolactone polyol product prepared from epsilon-caprolactone and trimethylolpropane polyether.
3. A method of preparing a deoiled puff leave-on dry hair spray of claim 1, wherein: the isocyanate substance is any one or more of toluene diisocyanate, diphenylmethane diisocyanate, 4' -diisocyanate dicyclohexylmethane, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
4. A method of preparing a deoiled puff leave-on dry hair spray of claim 1, wherein: the isocyanate substance is a modified polyisocyanate having an isocyanurate group of 3 or more based on one or more of toluene diisocyanate, diphenylmethane diisocyanate, 4' -diisocyanate dicyclohexylmethane, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
5. A method of preparing a deoiled puff leave-on dry hair spray as claimed in claim 1 wherein in step 3: in the premixing, 2 parts of silane coupling agent is added into the core of the starch granule, and after the starch granule is uniformly stirred and mixed, the high-activity polyether glycol is added.
6. A method of preparing a deoiled puff leave-on dry hair spray as claimed in claim 1 characterized by step 4: the number of isocyanate groups of the isocyanate substance added in the mixing reaction and the number of hydroxyl groups of the high-activity polyether polyol added in the step 4 are respectively 1.05-1.10 in the theoretical value ratio.
7. A method of preparing a deoiled puff leave-on dry hair spray as claimed in claim 1 characterized by step 4: when the isocyanate material added in the reaction was mixed, 1 wt% of N, N-dimethylformamide was previously mixed.
8. The method of preparing a deoiled fluff leave-on dry hair spray of any of claims 1 to 7, characterized in that:
the particle size range of the oil absorption particles is 0.1-30 microns.
9. The method of preparing a deoiled fluff leave-on dry hair spray of any of claims 1 to 7, characterized in that:
the oil absorption rate of the oil absorption particles is 60g/100 g-81 g/100 g.
10. The oil-removing fluffy washing-free hair drying spray is characterized by comprising the following components:
3-10 parts of oil-absorbing particles obtained by the preparation method of any one of claims 1-9; 0.5 part of butanediol; 0.5 part of glycerol; 0.5 part of EDTA disodium; 0.2 part of cetrimide; 0.2 part of tridecyl alcohol polyether-10; the balance being propellant.
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Cited By (1)
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| CN115645305A (en) * | 2022-10-31 | 2023-01-31 | 阳润科技(广东)有限公司 | Powder for fixing cosmetics and its preparing process |
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